US3607337A - Process for the production of organically modified silicic acids and silicates - Google Patents

Process for the production of organically modified silicic acids and silicates Download PDF

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US3607337A
US3607337A US765683A US3607337DA US3607337A US 3607337 A US3607337 A US 3607337A US 765683 A US765683 A US 765683A US 3607337D A US3607337D A US 3607337DA US 3607337 A US3607337 A US 3607337A
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wax
lacquer
silicic acid
weight
silicate
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Edith Eisenmenger
Otto Kuhnert
Robert Kuhlmann
Peter Nauroth
Guenter Tuerk
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DEUTCHE GOLD und SIBER SCHEIDE
DEUTCHE GOLD-UND SIBER-SCHEIDEANSTALT VORMATS ROESSLER
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DEUTCHE GOLD und SIBER SCHEIDE
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/152Preparation of hydrogels
    • C01B33/154Preparation of hydrogels by acidic treatment of aqueous silicate solutions
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • C09C1/30Silicic acid
    • C09C1/3072Treatment with macro-molecular organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • C09C1/30Silicic acid
    • C09C1/309Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08Treatment with low-molecular-weight non-polymer organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10Treatment with macromolecular organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/42Gloss-reducing agents
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/51Particles with a specific particle size distribution
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/10Solid density
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/60Optical properties, e.g. expressed in CIELAB-values
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • C01P2006/82Compositional purity water content
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/90Other properties not specified above

Definitions

  • ABSTRACT A process for modifying silicic acids, gels, and 54 PROCESS 1001;: THE PRODUCTION OF g f f f 1 Y ff'f fi ORGANlCALLY MODIFIED SllLlClC Acrns AND 9 p0 yet y i
  • the 1 gc SHLICATES silicates can be impregnated either as they are being formed or N D after they have formed by adding an aqueous emulsion or o rawmgs dispersion of wax or thermoplastic material to an aqueous [52] US. Cl 106/288 Q, suspension or dispersion of the sillicic acids, gels or silicates.
  • the invention relates to a process for the production of organically modified precipitated silicic acids and silicates, which are suitable particularly for delustering films of lacquers.
  • wax impregnated silicic acids do show a certain fineness in particle size, they no longer satisfy the requirements of modern lacquer and pigment technology and its in creasing demands with respect to lacquered surfaces, espe cially for surfaces coated with relatively thin films of pigmented lacquer.
  • the invention started with the task of finding a process for the production of organically modified, precipitated silicic acids and silicates through impregnation of the silicic acids and silicates with waxes or plastics to form products with improved dulling and deposit properties in clear varnishes (lacquers) or pigmented lacquers of all kinds.
  • lacquers clear varnishes
  • Such wax-impregnated compounds can be dispersed in the lacquers through simple stirring with a high speed mixer and remain suspended in the above-mentioned lacquers even during prolonged storage, or can be redispersed in the lacquer without difficulty in the event some of them do settle or deposit after storage.
  • the characterizing part of the invention is to be seen in the fact that during and/or after precipitation of silica gels or silicic acid or silicates from alkali silicate solutions in the presence of acids or metal salts, an aqueous emulsion of an in ert, colorless, high-melting wax or plastic is added, and the mixture is subsequently filtered, the filter cake is washed, dried, and finely ground.
  • the impregnation of the silicic acid or silicates can take place either by addition of the wax emulsion during the precipitation process or, after the precipitation of the silicic acid or silicates, by adding the proper quantity of a wax emulsion to the precipitation emulsion. It is also possible to add a part of the wax emulsion during, and another part after precipitation of the silicic acid or silicates.
  • any silicic gel or silicic acid, or silicate suspension can be impregnated with wax as a result of which the deposit behavior of the modified silicic acid or silicates in lacquers, as well as the resistance to scratching of the films of lacquers, is considerably improved as compared to other commercial, wax'modified, dulling silicic acids.
  • precipitated silicic acids and silicates include such substances that are formed directly by precipitation from alkali silicate solutions-preferably water glass and mineral acids or metal salt solutions. In this manner one can very easily obtain powdery, soft, and quickly dispersible dulling agents.
  • the delustering products, produced according to the invention are distinguished, in comparison to former similar commercial products, by a qualitatively particularly good surface of the dulled layers of lacquer, which can be traced back to the comparatively greater fineness of the products.
  • the modified silicic acids or silicates, obtainable according to the method of the invention show, in comparison with similar commercial, waxcontaining silicic acids, surprisingly no particular thickening effect on the lacquers, despite their fine grain size which has a favorable effect on the course of the dull lacquer during spraying.
  • the capability for very fine dispersion of the dulling products of the invention permits spraying of lacquers to form thinner films. This is particularly desirable in the case of dullclear varnishes used in the furniture industry. Thinner films of lacquer deluster better, as a rule, than thicker ones, which leads, or can lead, to an additional increase of the dulling power.
  • For the production of dull-clear varnishes one would used the modified silicic acid because of the transparency which is required, whereas, because of their decreased transparency characteristics, modified silicates are used for pigmented dull lacquers.
  • the process can also be carried out with an aqueous dispersion of a plastic material which can be used instead of the above wax emulsion for the impregnation of the silica gels or silicic acids and silicates.
  • a plastic material which can be used instead of the above wax emulsion for the impregnation of the silica gels or silicic acids and silicates.
  • synthetic lacquer dispersions Through treatment with such synthetic lacquer dispersions, one can likewise produce modified products with good deposit behavior.
  • the plastic material be completely inert in the water or the lacquer systems, that it be insoluble in water, and, finally, that it be so fine, about 7 to 10 microns or less, that it can be put into a stable dispersion form.
  • finely dispersed polyethylene can be changed into a stable dispersion form without trouble in the presence of surface active substances and can be used for the purposes of the invention.
  • the process is not limited to this plastic material or synthetic substance; polyvinylchloride, Teflon (polytetrafluoroethylene), and other thermoplastic compounds also can be used in the dispersed form.
  • Machine devices which are suitable for carrying out such a step in the process, such as dispergators, are frequently used in chemical engineering. Recently, such dispergators have become available as continuously operating machines with high feed performance, so that it will be possible to continuously and very intensively mix any desired silicic acid or silicate suspension with the wax emulsion or dispersion of a synthetic substance.
  • waxes such as natural waxes of animal or vegetable origin, such as mineral waxes, as well as synthetic waxes
  • waxes are chosen which are distinguished by insolubility in lacquer solvents, a high melting point of more than 85 C. (hard waxes), a refractive index close to 1.50, and a relatively high decomposition temperature in the air (about 150 C).
  • synthetic substances too are to be used, which in the dispersed form have these characteristics.
  • the products according to the invention can also be used as fillers in the most varied areas, beside their suitability as dulling agents.
  • EXAMPLE 1 liters of sulfuric acid, density 1.058, are fed in at opposite points simultaneously, while stirring the mixture with a flat paddle mixer for minutes. The temperature is kept at 80 C. through regulation of the steam supply. Furthermore, a pH value of about 10 is maintained in the suspension through regulation of the acid supply during the entire precipitation.
  • a highly fluid, transparent, white suspension with a solids content of about 45 g/l is obtained.
  • the emulsion which forms is introduced into the silicic acid mixture while stirring and after cooling. The stirring is continued for about 30 minutes. Afterwards, the mixture is filtered off in the customary manner via a filter press. The drying of the pressed dough is accomplished in a belt drier at a recirculated air temperature of about 105 C.
  • a white granulate is obtained which can easily be crushed into a fine powder.
  • the product is ground in a suitable mill into fine powder.
  • the lacquer is filled into closable glass flasks for observation of sedimentation behavior. After a standing time of 8 weeks, the lacquer showed no deposit whatever on the bottom.
  • the above-men tioned lacquer is treated with 14 of 10% alcoholic l-[Cl solution and is sprayed in the known manner onto primed wooden boards.
  • the degree of luster of example hardened film of lacquer is determined according to Lange.
  • the intensity of the reflected light is measured, whereby the reflected share of a ray of light striking the lacquer coating at a 45 angle is determined photoelectrically.
  • the degree of luster in the case of the silicic acid made according to the invention amounted to 7%.
  • the commercial dulling agent on the other hand had a degree of luster of 10%.
  • the dulling agent produced according to the invention was clearly superior to the commercial agents with regard to scratch resistance.
  • EXAMPLE 2 A silicic acid produced according to Example 1 was covered in the described manner through addition of a fairly large quantity of emulsion with 5% polyethylene wax. After filtering and drying, soft, uniformly pale yellow colored pieces were obtained. These were ground fine in a suitable grinder.
  • the film made with this lacquer using the silicic acid ac cording to the invention was completely free of spots and extremely scratch resistant. It had a degree of luster of 8%.
  • the film of lacquer made with the comparison product was softer and less scratch-resistant. It only had a degree of luster of 14%.
  • EXAMPLE 3 4.2 liters of water are placed in a closed stirrer with 30-liter capacity, provided with a reflux cooler, made of acid-resistant steel. This is heated indirectly to 60 C. with a gas burner, and is kept at this temperature during precipitation. Then a solution of water glass, thinned down to 13% by weight of SiO content (mole ratio 113.36) is added and, as soon as a pH value of 12 has been reached in the initial mix, an aluminum sulfate solution with 1.4% by weight of A1 0 content is permitted to run in at a place opposite to the place of entry of the silicate solution.
  • the solutions reacting one with another are measured by means of a flow meter in such a manner that 12.6 liters of silicate solution and 11.6 liters of aluminum sulfate solution are added in 100 minutes.
  • the suspension is stirred with a flat paddle stirrer (diameter 20 cm., height cm., rotating at 50 to 70 r.p.m.) During the precipitation, a pH value of about 12 is maintained in the medium through regulation of the influx speed of the aluminum sulfate solution. After 100 minutes the precipitation is completed.
  • a wax emulsion is produced by allowing 210 g. of melted hard paraffin to run into 1 liter of water at 90 C. to which is added, as an emulsifier, 5 g. of cetyltrimethylammonium bromide, and 25 g. of a silicic acid, precipitated according to example l, is added.
  • the finished emulsion is placed into the aluminum silicate suspension while stirring. Then the suspension is adjusted to about pH 4 through addition of an aluminum sulfate solution. The precipitate is filtered off, washed, dried at 105 C. and ground fine on a suitable grinder. 2320 g. of a white, soft powder is obtained.
  • silicic acid suspension was adjusted to a pH value of 3.5 with 55.5% sulfuric acid (density: 1.45 g/cm), which was accomplished by means of a 35 minute influx of acid at a rate of 2.5 liters/hour.
  • PAD was 521 20% by weight) melt Genapol-S-l50 1% by weight) Arkopal N-090 4% by weight) KOH solution 1.4% by weight) initial Water 73.6% by weight) 1.3 liters of this 20% wax emulsion were added to the original suspension during a period of 15-20 minutes while stirring.
  • EXAMPLE 5 For precipitation, 67.5 liters of hot water, 3 liters of a 20% PAD Wax 521 emulsion, and 10.48 liters of sodium silicate (density: 1.17 g/cm, modulus: SiO Na O 3.30) were heated while stirring.
  • sodium silicate (density: 1.35 g/cm: modulus: SiO Na O 3.30) was added at the rate of 1.9 liters/hour to the alkaline initial precipitate while stirring and dispersing (with a dispergator pump of the type Dispax-Reactor 6/3/3). During this reaction phase, the precipitation suspension passed 30 times through the dispergator pump.
  • the wax-silicic acid suspension was finally adjusted to a pH value of 3. 5 with 55.5% sulfuric acid (density 1.45 g/cm) which was accomplished by means of a 35 minute influx of acid at a rate of 2.5 liters/hour while the mixture was stirred and dispersed.
  • the washed filter cake was dried for 12 hours at 1 10-120" C and subsequently ground in a suitable grinder (Sicht-muehle.)
  • the wax-impregnated precipitation produce represented a very finely dispersed, white, freely flowing powder, which could be characterized as follows:
  • pH value in 4% aqueous suspension 5.20
  • EXAMPLE 6 A modified silicic acid is produced in the manner set forth in example 5. The only difference is the treatment of the precipitation suspension, which in this case is made without the use of the dispergator.
  • the modified silicic acid obtained has the following characteristics:
  • EXAMPLE 8 For the production of a wax modified dulling silicic acid, the same procedure was followed as in example 4. However, a part of the wax emulsion used, to wit 0.86 liter, was added to the initial substance, so that a precipitation modified silicic acid suspension developed which, after acid adjustment, was treated with an additional 2.14 liters of wax emulsion in the course of -20 minutes, while stirring. The silicic acid obtained in accordance with this example was produced without the use of a dispcrgator.
  • pH value in 4% aqueous suspension 5.60 Density at 25 C.: 1.89 g./cm.
  • Bulk Weight 60 g./l.
  • the lacquer was used without hardening acid addition.
  • the quantity of dulling agent worked into the lacquer amounted to 2.5% by weight.
  • Nitro-Combination Lacquer Parts by weight Nitrocellulose (Wool E 510") The quantity of dulling agent worked into the lacquer amounted to 1% by weight.
  • the dulling material produced according to the invention can easily be redispersed through slight shaking of the test lacquer by hand, even after long storage times.
  • the SH lacquer it is superior even to the wax-modified dulling agent produced according to the status of the prior art.
  • Nonmodified silicic acids settle in a hard cake and cannot be dispersed again.
  • these favorable sedimentation characteristics can be achieved on the basis of the new improved process of impregnation even with relatively small quantities of wax, which makes the process an economic one. Beyond that, the clearly smaller quantity of wax increases the hardness and scratch-resistance of the films of lacquer, so that the dulling silicic acids according to the invention are superior to the ones synthesized in accordance with the status of the prior art.
  • the glossimeter according to B. Lange which is frequently used in Germany, is used for the determination of degree of luster, which represents a measure for the delustering power of dulling silicic acid tested.
  • degree of luster which represents a measure for the delustering power of dulling silicic acid tested.
  • the Lange glossimeter uses an angle of 45 as an angle of incidence and reflection.
  • the measured degrees of luster are stated in percent. The smaller their value, the better will be the delustering capacity of the silicic acid tested, or, in other words, less dulling agent will need be used in order to achieve a certain degree of luster.
  • the determination of grindometrid value is made with the help of a grindorneter.
  • the grindometric value which is measured in t, is a measure for the coarsest particles which occur in the finished, sprayable lacquer mixture after the dulling silicic acid has been stirred in. It can be brought into a relationship with the formation of spots in the dry film of lacquer. The feared and undesirable spraying grain (Spritzkorn) can be spotted with the help of the grindometer. All the grindometer measurements shown in Table 11 were made in black enamel, which was sprayed in a thickness of about 35 11. per layer. The compositions of the four lacquers in which the dulling capacity of the silicic acids of the invention were tested are given below.
  • Black alkyd resin enamel The following were mixed into a paste on the triple roller: 450.0 parts of oil alkyd resin (Alkydal ST”) (75% in xylene) 1.8 parts of soya lecithin 80.0 parts of n-butanol 9 Q.
  • Polyester resin lacquer (UPE lacquer) 1040 parts of polyester resin (Rnskydal 500B") 260 parts of olyester resin (Roskydal S00") 64 parts of silicon oil (0L) (1% in toluene) 5 72 parts of monostyrcnc 1936 parts 96.8 g. of the above lacquer mixture, 3.2 g. of accelerator (Co-Naphtenat 10% in toluene), 6.5 g. of dulling agent, and 10 g.
  • UPE lacquer 1040 parts of polyester resin (Rnskydal 500B") 260 parts of olyester resin (Roskydal S00”) 64 parts of silicon oil (0L) (1% in toluene) 5 72 parts of monostyrcnc 1936 parts 96.8 g. of the above lacquer mixture, 3.2 g. of accelerator (Co-Naphtenat 10% in toluene), 6.5 g. of dulling agent, and 10
  • hardener organic peroxide AP/20% in ethyl acetate
  • hardener organic peroxide AP/20% in ethyl acetate
  • the lacquer was sprayed to form a layer having a thickness of 80-1 00/.L.
  • the four described test lacquers containing the dulling silicic acids of examples 4-8 according to the invention without exception have lower degrees of luster than the known wax-modified types of silica gel.
  • the dulling (delustering) capacity increases in one case (acid hardening lacquer, example almost threefold, and in several other cases it increases twofold.
  • the values for the degree of luster in these cases came out particularly favorably in the SH lacquer, UPE lacquer, and the black enamel.
  • silicate precipitate with an aqueous emulsion or dispersion of a water-insoluble, inert wax, filtering the wax-impregnated precipitate, and finely grinding said precipitate, the amount of said wax on said silicic acid, silica gel, or silicate being about 0.5 to 15 percent by weight thereof.
  • Wax impregnated silicic acid, silica gel, or silicate granules wherein said wax is present in an amount of about 2 to about 10% by weight thereof and said granules are of a size of about 10 microns or less.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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US765683A 1967-10-12 1968-10-07 Process for the production of organically modified silicic acids and silicates Expired - Lifetime US3607337A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1592865A DE1592865C3 (de) 1967-10-12 1967-10-12 Verfahren zur Herstellung von organisch modifizierten Kieselsauren
DED0054748 1967-12-02

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BE (1) BE722073A (nl)
CH (1) CH531989A (nl)
FR (1) FR1585800A (nl)
GB (1) GB1236775A (nl)
NL (1) NL166275C (nl)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773535A (en) * 1972-02-25 1973-11-20 Ferro Corp Abrasion resistant stabilized lead chromate pigments coated with silica and polyolefin wax
US3808019A (en) * 1972-01-29 1974-04-30 Hoechst Ag Process for the preparation of pigment compositions for coloring polyolefins
US3816154A (en) * 1973-05-18 1974-06-11 Goury T Mc Silica gel flatting agent
US4038224A (en) * 1975-04-11 1977-07-26 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Organically modified silicic acids and silicates for delustering lacquers
US4166811A (en) * 1977-12-19 1979-09-04 Dominion Colour Company Ltd. Pigment compositions and methods of preparation
US4179431A (en) * 1978-01-30 1979-12-18 Deutsche Gold-und Silber-Scheideanstalt vormals Rosseler Precipitated silicic acid granules
US4263051A (en) * 1978-06-12 1981-04-21 Ppg Industries, Inc. Soft-settling silica flatting agent
US5110769A (en) * 1989-02-15 1992-05-05 W. R. Grace & Co.-Conn. Inorganic hydrogel flatting agents
US5221337A (en) * 1990-02-14 1993-06-22 W. R. Grace & Co.-Conn. SiO2 flatting agent, process for its production and its use
DE19814839A1 (de) * 1998-04-02 1999-10-07 Bayer Ag Hydrophobierte oxidische oder silikatische Füllstoffe enthaltende Emulsionskautschukmischungen sowie deren Verwendung zur Herstellung von Reifen
DE19818552A1 (de) * 1998-04-24 1999-10-28 Bayer Ag Mischungen aus Kautschuken und aktivierten und hydrophobierten exidischen und silikatischen Füllstoffen und ein Verfahren zur Herstellung
WO2000001775A1 (en) * 1998-07-03 2000-01-13 International Coatings Limited Powder coating compositions
US6103004A (en) * 1995-04-26 2000-08-15 Grace Gmbh Matting agent based on aggregated silica
US6251958B1 (en) * 1998-04-27 2001-06-26 Henkel Corporation Defoamer process
US6531524B2 (en) 1998-07-03 2003-03-11 International Coatings Limited Powder coating compositions
US20030121453A1 (en) * 2001-12-26 2003-07-03 Shiro Iwahashi Matting agent for paint and energy beam-hardening paint compound
US6770128B1 (en) 1999-04-13 2004-08-03 Grace Gmbh & Co. Kg Matting agent radiation for curing coatings
US20040204524A1 (en) * 2001-06-21 2004-10-14 Hubert Baumgart Solvent-containing mixtures which can be cured physically or thermally and/or by means of actinic radiation, method of production and use thereof
US20050065268A1 (en) * 2001-11-13 2005-03-24 Gemma Morea-Swift Silica matting agents
US20050175916A1 (en) * 2002-08-01 2005-08-11 Kittle Kevin J. Toner/developer compositions
WO2005111729A2 (de) * 2004-05-14 2005-11-24 Clariant Produkte (Deutschland) Gmbh Hydrophobiertes salzartiges struktursilikat
WO2005121258A1 (de) * 2004-06-11 2005-12-22 Clariant Produkte (Deutschland) Gmbh Hydrophobierte salze schichtartiger metallhydroxide
CN100519665C (zh) * 2002-09-06 2009-07-29 德古萨公司 基于沉淀二氧化硅的高效消光剂
EP3155033A1 (en) * 2014-06-16 2017-04-19 PQ Silicas UK Limited Curable liquid compositions
US11999857B2 (en) 2017-06-02 2024-06-04 W.R. Grace & Co.-Conn. Coated particles and methods of making and using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY158909A (en) 2006-12-07 2016-11-30 Grace Gmbh & Co Kg Matting agent

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US2838413A (en) * 1954-05-27 1958-06-10 Grace W R & Co Silica gel flatting agent, method of preparing same, and composition containing same
US3025179A (en) * 1957-03-28 1962-03-13 Thann Fab Prod Chem Organophilic and hydrophobic pigments and method for their preparation
US3074800A (en) * 1958-08-08 1963-01-22 Doleo S A Writing or painting substance for ball point pens and similar devices

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US2838413A (en) * 1954-05-27 1958-06-10 Grace W R & Co Silica gel flatting agent, method of preparing same, and composition containing same
US3025179A (en) * 1957-03-28 1962-03-13 Thann Fab Prod Chem Organophilic and hydrophobic pigments and method for their preparation
US3074800A (en) * 1958-08-08 1963-01-22 Doleo S A Writing or painting substance for ball point pens and similar devices

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808019A (en) * 1972-01-29 1974-04-30 Hoechst Ag Process for the preparation of pigment compositions for coloring polyolefins
US3773535A (en) * 1972-02-25 1973-11-20 Ferro Corp Abrasion resistant stabilized lead chromate pigments coated with silica and polyolefin wax
US3816154A (en) * 1973-05-18 1974-06-11 Goury T Mc Silica gel flatting agent
US4038224A (en) * 1975-04-11 1977-07-26 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Organically modified silicic acids and silicates for delustering lacquers
US4166811A (en) * 1977-12-19 1979-09-04 Dominion Colour Company Ltd. Pigment compositions and methods of preparation
US4179431A (en) * 1978-01-30 1979-12-18 Deutsche Gold-und Silber-Scheideanstalt vormals Rosseler Precipitated silicic acid granules
US4263051A (en) * 1978-06-12 1981-04-21 Ppg Industries, Inc. Soft-settling silica flatting agent
US5110769A (en) * 1989-02-15 1992-05-05 W. R. Grace & Co.-Conn. Inorganic hydrogel flatting agents
US6696375B2 (en) 1989-02-15 2004-02-24 W. R. Grace & Co.-Conn. Inorganic hydrogel flatting agents
US5221337A (en) * 1990-02-14 1993-06-22 W. R. Grace & Co.-Conn. SiO2 flatting agent, process for its production and its use
US6103004A (en) * 1995-04-26 2000-08-15 Grace Gmbh Matting agent based on aggregated silica
DE19814839A1 (de) * 1998-04-02 1999-10-07 Bayer Ag Hydrophobierte oxidische oder silikatische Füllstoffe enthaltende Emulsionskautschukmischungen sowie deren Verwendung zur Herstellung von Reifen
US6313211B1 (en) 1998-04-02 2001-11-06 Bayer Aktiengesellschaft Emulsion rubber mixtures containing hydrophobic-rendered oxide or silicate type fillers and their use for producing tires
DE19818552A1 (de) * 1998-04-24 1999-10-28 Bayer Ag Mischungen aus Kautschuken und aktivierten und hydrophobierten exidischen und silikatischen Füllstoffen und ein Verfahren zur Herstellung
US6251958B1 (en) * 1998-04-27 2001-06-26 Henkel Corporation Defoamer process
US20020169234A1 (en) * 1998-07-03 2002-11-14 International Coatings Limited Powder coating compositions
US6531524B2 (en) 1998-07-03 2003-03-11 International Coatings Limited Powder coating compositions
US7019051B2 (en) 1998-07-03 2006-03-28 International Coatings Limited Powder coating compositions
WO2000001775A1 (en) * 1998-07-03 2000-01-13 International Coatings Limited Powder coating compositions
US6770128B1 (en) 1999-04-13 2004-08-03 Grace Gmbh & Co. Kg Matting agent radiation for curing coatings
US20040204524A1 (en) * 2001-06-21 2004-10-14 Hubert Baumgart Solvent-containing mixtures which can be cured physically or thermally and/or by means of actinic radiation, method of production and use thereof
US20050065268A1 (en) * 2001-11-13 2005-03-24 Gemma Morea-Swift Silica matting agents
US20030121453A1 (en) * 2001-12-26 2003-07-03 Shiro Iwahashi Matting agent for paint and energy beam-hardening paint compound
US20050090585A1 (en) * 2001-12-26 2005-04-28 Shiro Iwahashi Method of forming energy beam-hardening paint composition
US20050175916A1 (en) * 2002-08-01 2005-08-11 Kittle Kevin J. Toner/developer compositions
US7601472B2 (en) 2002-08-01 2009-10-13 Akzo Nobel Coatings International B.V. Toner/developer compositions
CN100519665C (zh) * 2002-09-06 2009-07-29 德古萨公司 基于沉淀二氧化硅的高效消光剂
WO2005111729A3 (de) * 2004-05-14 2006-06-08 Clariant Produkte Deutschland Hydrophobiertes salzartiges struktursilikat
US20080107986A1 (en) * 2004-05-14 2008-05-08 Eduard Michel Hydrophobic, Salt-Like Structured Silicate
WO2005111729A2 (de) * 2004-05-14 2005-11-24 Clariant Produkte (Deutschland) Gmbh Hydrophobiertes salzartiges struktursilikat
US20080070139A1 (en) * 2004-06-11 2008-03-20 Eduard Michel Hydrophobic Salts of Layered Metal Hydroxides
WO2005121258A1 (de) * 2004-06-11 2005-12-22 Clariant Produkte (Deutschland) Gmbh Hydrophobierte salze schichtartiger metallhydroxide
CN101048467B (zh) * 2004-06-11 2011-01-12 科莱恩产品(德国)有限公司 层状金属氢氧化物的疏水化盐
US7923189B2 (en) 2004-06-11 2011-04-12 Clariant Produkte (Deutschland) Gmbh Hydrophobic salts of layered metal hydroxides
JP4810535B2 (ja) * 2004-06-11 2011-11-09 クラリアント・プロドゥクテ(ドイチュラント)ゲーエムベーハー 層状金属水酸化物の疎水性塩
EP3155033A1 (en) * 2014-06-16 2017-04-19 PQ Silicas UK Limited Curable liquid compositions
US11999857B2 (en) 2017-06-02 2024-06-04 W.R. Grace & Co.-Conn. Coated particles and methods of making and using the same

Also Published As

Publication number Publication date
BE722073A (nl) 1969-03-14
GB1236775A (en) 1971-06-23
NL6814075A (nl) 1969-04-15
NL166275B (nl) 1981-02-16
CH531989A (de) 1972-12-31
NL166275C (nl) 1981-07-15
FR1585800A (nl) 1970-01-30

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